ChemComm
Communication
This work was financially supported by KAKENHI
(24106745) from MEXT. A.N. thanks JSPS for a predoctoral
fellowship.
Notes and references
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Fig. 4 Profile of the reaction of 2 with 3 promoted by 1c. Black squares represent
yields of 4. 2: 0.1 mmol, 3: 0.12 mmol, solvent 1.5 mL. Green, blue, and red bars
represent the amount of trans-1c + cis-1c, trans-1c, and cis-1c in the solution phase,
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rapid reaction progress was observed to afford 80% of 6 after
100 min.12,13
In conclusion, we developed a photoswitchable nucleophilic
catalyst based on aggregation/dissociation of a diamide frame-
work. The catalyst on–off state could be manipulated in the
course of the reaction by UV/Vis irradiation. Installation of
other catalytically active functional groups to produce distinct
photoswitchable catalysts is currently underway.
5 For general utility of 1a and its analogue in asymmetric catalysis:
N. Kumagai and M. Shibasaki, Angew. Chem., Int. Ed., 2013, 52,
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9 Trans/cis = 4/96 at the photostationary state.
10 See ESI† for details.
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12 6 was obtained in 7.8% ee and 14.5% ee by trans-(S)-1c and cis-(S)-1c,
respectively (the (S)-isomer was obtained as a major product).
13 A small amount of 3-phenyl-2-benzofuranone was associated as a
byproduct.
Fig. 5 Profile of the rearrangement of 5 to 6 promoted by trans-1c (blue square)
and cis-1c9 (red circle). 5: 0.06 mmol, solvent 1.5 mL.
c
4630 Chem. Commun., 2013, 49, 4628--4630
This journal is The Royal Society of Chemistry 2013